CA2452522A1

CA2452522A1 - Dyes incorporating anionic and cationic groups

Info

Publication number: CA2452522A1
Application number: CA002452522A
Authority: CA
Inventors: Michael Lennartz; Doelf Kaeser; Sandra Weiss
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 2001-07-20
Filing date: 2002-07-11
Publication date: 2003-02-06
Also published as: US20040205912A1; CN1533416A; KR20040018490A; CN1289608C; WO2003010239A1; EP1442082A1; JP2004536202A; US7066969B2; MXPA04000171A; ZA200309589B; BR0211272A

Abstract

The present invention relates to novel compounds of the formulae [insert formula here] A, D1, D2, R1 and n are as defined in the description the compounds being in an internal or external salt form, or mixtures of compounds (1) and (2), a process for their preparation and preparations containing them used for dyeing paper.

Description

Dyes Incorporatina Anionic and Cationic Groups The present invention relates to dyes of the formula OH
A~N~N \ \ D1 / /
H03S i N i (1 ) or R N ~N~
D
R1 n N N~D~
OH
q~ ~~N NI i N
N ~ \ \
/ / n in which A represents a benzene sulphonic acid residue which is unsubstituted or substituted by one single hydroxy, halogen, amino, nitro, C,-C4alkyl, C,-C4alkoxy, C2-C4hydroxyalkoxy, COOC,-C4alkyl or NHCOC,-C4alkyl group, a benzoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C,-C4alkyl, C,-CQalkoxy, CZ-C4hydroxyalkoxy, COOC,-C4alkyl or NHCOC,-C4alkyl groups, a naphthalene sulphonic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C,-C4alkyl, C,-C4alkoxy, C2-C4hydroxyalkoxy, COOC,-C4alkyl or NHCOC,-C4alkyl groups or a naphthoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C,-C4alkyl, C,-C4alkoxy, CZ-C4hydroxyalkoxy, COOC,-C4alkyl or NHCOC,-Caalkyl groups;
D, and D2, independently represent i) a residue of the formula -NR~BX (3), in which B represents a C2-C8alkylene bridge which may be interrupted by a heteroatom, whereby C3-Csalkylene is branched or unbranched, a C2-Csalkylene bridge which is substituted by one or more hydroxy groups, a C,-Csalkylene-1,3- or -1,4-phenylene bridge or a 1,3-or -1,4-phenylene bridge;
R~ represents hydrogen or C,-C4alkyl unsubstituted or mono-substituted by hydroxy, halogen, cyano or C~-C4alkoxy;
X is a group of the formula -NR2R3, wherein R2 and R3, independently, represent hydrogen, C,-C4alkyl; C2-Csalkyl which is mono-substituted by hydroxy or by cyano, phenyl or Ci-C4alkylphenyl, whereby the phenyl ring of the latter two groups is unsubstituted or substituted by up to three groups selected from hydroxy, halogen, C,-C4alkyl and C~-C4alkoxy or, alternatively, RZ and R3, together with the nitrogen atom to which they are connected, complete a saturated, 5- or 6-membered ring which may contain, in addition to the nitrogen atom, one nitrogen or oxygen atom and which may be further substituted or, alternatively, X is a group of the formula -N+R4RSR6, wherein R4, R5 and R6 each, independently, represent C,-C4alkyl, C2-Csalkyl which is mono-substituted by hydroxy or by cyano, phenyl or C,-C4alkylphenyl, whereby the phenyl ring of the latter two groups is unsubstituted or substituted by up to three groups selected from hydroxy, halogen, C,-CQalkyl and C,-C4alkoxy or, ii) alternatively, D, and D2 independently represent a 5- or 6-membered, saturated heterocyclic ring connected by way of a nitrogen atom to the triazine ring and which ring may contain, in addition to the nitrogen atom, one further nitrogen or oxygen atom and which may be further substituted, whereby the nitrogen atom may be quaternised with a residue R4, Ra being as previously defined, and nis0orl, the compound being in an internal or external salt form, or mixtures of compound (1 ) and (2).
The residues D, and D2 are preferably identical.

Within the scope of the compound of formula (1 ), one preferred group of compounds are those in which n is 0, whilst those in which n represents 1 may also be preferred.
Furthermore, within the scope of the compound of formula (2), one preferred group of compounds are those in which n is 0, whilst those in which n represents 1 may also be preferred.
The residue A in the compounds of formula (1 ) and (2) may preferably represent a benzene sulphonic acid group which is unsubstituted or substituted by one single amino, nitro, halogen, hydroxy, C,-C4alkyl, C,-C4alkoxy or NHCOC1-C4alkyl group, a benzoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C,-C4alkyl, C,-C4alkoxy or NHCOC1-C4alkyl groups, a naphthalene sulphonic acid residue or a naphthoic acid residue.
When A represents a naphthalene sulphonic acid residue, this is preferably a 1-naphthalene-2-, 3-, 4-, 6-, 7- or 8- or a 2-naphthalene-1-, 5-, 6- or 7-sulphonic acid residue which is not further substituted, whilst when A represents a benzene sulphonic acid group, this is preferably a benzene-2-,3- or 4-sulphonic acid residue which is unsubstituted or substituted by one single amino, acetylamino, chloro, hydroxy, nitro, methyl or methoxy group, whilst when A represents a benzoic acid group, this is preferably a 2-, 3- or 4-benzoic acid residue which is unsubstituted or substituted by one or two acetylamino, hydroxy, chloro, amino, nitro, methyl or methoxy groups and when A represents a naphthoic acid residue, this is preferably a 2-substituted 1- or 3-naphthoic acid residue which is not further substituted.
When, in the compound of formula (1 ) or (2), Di and D2 represent a group of the formula -NRiBX (3), the residue B preferably represents a C2-Csalkylene bridge which is unbranched or, in the case of C3-Csalkylene, branched, and which may be substituted by a hydroxy group and, especially, a C2-C4alkylene bridge which is unbranched or, in the case of C3-C4alkylene,_ branched, and may be substituted by a hydroxy group, R, represents hydrogen or C,-C4alkyl, in particular, methyl and X is a group of the formula NRZR3 or -N+R4R5R6, wherein Rz and R3, independently, represent hydrogen or C,-C4alkyl, in particular, methyl or ethyl and R4, R5 and R6 each, independently, represent C,-CQalkyl, especially methyl or ethyl.
When, in the compound of formula (1) or (2) D~ and D2 represent a 5- or 6-membered, saturated heterocyclic ring, this is preferably an -N-pyrrolidino, -N-morpholino, -N-piperidno or -N-piperazino residue, whereby the piperazino ring may be further substituted by C,-C4alkyl, C,-C4aminoalkyl or C1-C4hydroxyalkyl on the nitrogen atom in the 4-position, as exemplified by a -1-substituted 4-methylpiperazino, 4-(2-aminoethyl)piperazino or a 4-(2-hydroxyethyl)piperazino residue. When the nitrogen atom of the ring is quaternised with a group R4, this is preferably a C,-CQalkyl group, more preferably, methyl or ethyl, as exemplified by an N-methyl or N-ethyl piperidinium, pyrrolidinium or morpholinium residue.
Alternatively, the nitrogen atom in the 4-position of the piperazine nucleus may be substituted by a C2-Csalkyl residue which, in turn, is further substituted by a quaternary ammonium group as, for example, a 1-substituted-4-(2-triethyl- or trimethyl)ethyl- or propylammonium piperazino residue.
An especially preferred embodiment of the invention is represented by the compound of formula (1) in which A represents a 1-naphthalene-6-sulphonic acid, a 2-naphthalene-6-sulphonic acid or a 2-naphthalene-7-sulphonic acid residue, B represents an n-propylene or an isopropylene residue, R1 represents hydrogen, X is a diethylamino or an amino (-NHZ) residue and n is 0, the compound being in an internal or external salt form.
Within the scope of the definitions of the compounds of formulae (1) and (2), C,-C4alkyl groups may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, whilst C1-C4alkoxy groups may be exemplified by methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy groups. Examples of C2-C4hydroxyalkoxy are 2-hydroxyethoxy, hydroxy-n- or isopropoxy and hydroxy-n-, sec-,iso- or tert-butoxy.
Haologen, in compounds of formulae (1 ) and (2) is iodine, bromine, fluorine or, especially, chlorine.
A C2-Cealkylene bridge in the definition of B may, for example be an ethylene, n-propylene, methyl ethylene, 1- or 2-methyl propylene, n-butylene, ethyl ethylene, n-pentylene, ethyl propylene, dimethyl propylene, methyl butylene, n-hexylene, dimethyl butylene, methyl pentylene, ethyl butylene, n-heptylene, methyl hexylene, dimethyl pentylene, ethyl pentylene, trimethyl butylene, n-octylene, methyl heptylene, dimethyl or ethyl hexylene or a trimethyl pentylene bridge, which may be interrupted by a heteroatom, preferably selected from nitrogen, oxygen or sulphur.
A C,-Csalkylene-1,3- or 1,4-phenylene bridge may be a 1,3- or 1,4-phenylenemethylene, phenyleneethylene, phenylenepropylene, phenylenebutylene, phenylenepentylene or phenylenehexylene residue.
Where, in the definitions of the substituents R2, R3, R4, R5 and/or R6 as C2-Csalkyl which is mono-substituted by hydroxy or by cyano, these may be hydroxy- or cyanoethyl, hydroxy- or cyanopropyl, hydroxy- or cyanobutyl, hydroxy- or cyanopentyl or hydroxy- or cyanohexyl, whilst Ci-C4alkylphenyl may be benzyl, phenethyl, propylphenyl or butylphenyl groups.
The dyes of the formulae (1 ) and (2) may be prepared by known methods, for example, by reacting the diazonium salt of an amine of the formula A-NH2 (4) with a compound of the formula OH
\ \ D1 H03S i ~ i (5) or R .N

R N N~D1 ~N
n~

whereby A, R,, D1, D2 and n are as previously defined.
Such reactions for the preparation of azo-dyes are well documented in the chemical literature.
In certain cases in which the dyes of the formulae (1) and (2) contain free amino groups, it is advantageous to introduce a protective group which, after the coupling reaction, is then removed. Suitable protective groups are those which are readily cleaved, but are stable under the conditions of the azo-coupling reaction. Especially suitable groups are, for example, carboalkoxy groups, in particular, the carbomethoxy or carboethoxy groups or acyl groups suchas propionyl or , in particular, acetyl groups.
The intermediate compounds of the formulae (5) and (6) are known compounds or may be prepared according to known methods, for example by stepwise reaction, in any desired sequence, of cyanuric chloride with an amine of the formula D, H (7) and/or DZH (8) and with a further amine of the formula N
(9) or R N H
R, ~n _7_ HO

N
~H H
w w ~ (10), n /~/
whereby R,, D,, D2 and n are as previously defined.
The dyes of the invention may be used to dye natural or synthetic materials, but are particularly useful for dyeing paper. They are preferably used as a solid or liquid commercial form.
The pulverulent or granular form of the dye is used particularly in batch-wise pulp dyeing where the dye mixture, customarily in the form of a stock solution, is added in the pulper, in the beater or in the mixing chest. Preference is here given to using dye preparations which as well as the dye, may further include extenders, for example urea as solubilizer, dextrin, Glauber salt, sodium chloride and also dispersants, dust-proofing agents and sequestrants, such as tetra-sodium phosphate.
The present invention accordingly further provides solid dye preparations for dyeing paper comprising a compound of the formula (1 ) and/or (2) and, optionally, further auxiliaries.
In recent years, the use of concentrated aqueous solutions of dyes has gained importance because of the advantages possessed by such solutions when compared with dyes in powder form. The use of solutions avoids the difficulties associated with dust formation and releases the user from the time-consuming and frequently difficult dissolving of the dye powder in water. The use of concentrated solutions was also prompted by the development of continuous dyeing processes for paper, since it is convenient in these processes to meter the solution directly into the pulp stream or to add it at some other suitable point of the paper-making process.

_g-The present invention accordingly further provides aqueous solutions, preferably concentrated solutions, for dyeing paper, comprising a compound of the formula (1 ) and/or (2), preferably in a concentration of from 5 to 30% by weight. Due to their excellent solubility in water, the dyes of formula (1 ) and (2) are particularly suitable for the preparation of such solutions.
The concentrated solutions preferably contain a low level of inorganic salts, which may be achieved, if necessary, by known methods, for example reverse osmosis.
The solutions may include further auxiliaries, for example solubilizers such as E-caprolactam or urea, organic solvents, for example glycols, polyethylene glycols, dimethyl sulphoxide, N-methylpyrrolidone, acetamide, alkanolamines or polyglycolamines, which is a still further aspect of the invention.
The novel dyes of the invention dye paper in predominantly red shades with a high degree of exhaustion under particular dyeing conditions. The resulting dyeings exhibit excellent fastness to water and to light.
Consequently, one further aspect of the invention is paper which is dyed with a compound of the formula (1 ) and/or (2), either in the form of a solid dye preparation, or an aqueous solution, as described above.
The following Examples serve to illustrate the invention without intending to be restrictive in nature. Parts and percentages are by weight unless otherwise stated.

_g_ Example 1 OH HN~~N~
N%N \ \ N N
\ ( ~ / / ~''/~ ~ ( 101 ) Step 1 184g of cyanuric chloride are added to 250g of water and 250g of ice and the mixture stirred for 30 minutes. To the resulting white suspension, 260g of N,N-diethylaminopropylamine are added with stirring over 3.5 hours, the temperature being maintained at 5°C. After the addition, the temperature is raised to 45-50°C, the mixture stirred for a further 1 hour and the pH then raised to 9.5-9.9 by the addition of approximately 180m1 of 30%
aqueous sodium hydroxide. The resulting white precipitate is filtered with suction, washed with water and dried under vacuum at 50°C to yield 276.6g of 2,4-diamino-N,N'-bis-(3-diethylaminopropyl)-6-chloro-1,3,5-triazine.
2348 of the 2,4-diamino-N,N'-bis-(3-diethylaminopropyl)-6-chloro-1,3,5-triazine thus obtained are dissolved in 1025m1 of water and 124m1 of concentrated hydrochloric acid and 143.3g of 6-amino-1-naphthol-3-sulphonic acid added. The mixture is then stirred for 1 hour at 85°C, the pH being maintained at 2.5 by the addition of 4N aqueous sodium hydroxide and then cooled to room temperature. There is obtained 17458 of a clear brown solution containing 3448 of the compound of formula OH HN~N~
\ \ N' \ N
~~ ~ (100) By replacement of the N,N-diethylaminopropylamine by equivalent quantities of the appropriate amines and proceeding in an analogous manner, the following intermediates of formula D' OH
N ~N
/ / (11 ) H03S H N D' may be obtained, as summarized in Table 1.
Table 1 Example (100a) (100b) (100c) (100d) (100e) (1 OOf) Nr:

H
/N~NH /N~NHZ N~ NON ~N~N~ N
i ~

z / NHz Example (100g) (100h) (100i) (100j) (100k) (1001) Nr-_ _ _ _ N N

/N NHZ ~ - ~ H - ~ - U ~ ~--~
/N~ OH ~
NH

D,.', . Z
.

Step 2 4.46g of 1-naphthylamine-6-sulphonic acid are dissolved in 30m1 of water and approximately 0.5m1 of 50% aqueous sodium hydroxide and treated with 5m1 of concentrated hydrochloric acid. To the resulting fine suspension, 5m1 of a 4N aqueous sodium nitrite solution are then added slowly, the temperature being maintained at 5°C. After stirring for 30 minutes at this temperature, the excess nitrite is destroyed by the addition of a little sulphamic acid. The resulting diazonium salt suspension is then added dropwise at 10°C to 87.28 of the solution of compound (100) obtained in Sfepl above, the pH being maintained at 6.6 by addition of approximately 12m1 of 2N aqueous sodium hydroxide. After salting out, there are obtained 9.9g of the compound of formula (101 ), which dyes paper with a high degree of exhaustion in red shades with excellent water fastness.

Example 2 / / ~ OH HN~N~
\ \ NON \ \ N N
H03S I / / (102 H03S H N H~ N~
1.34g of 2-naphthylamine-7-sulphonic acid are slurried in 100m1 of water and 3g of 32%
aqueous hydrochloric acid added. After cooling to 5°C, 1.5m1 of 4N
aqueous sodium nitrite solution are slowly added at this temperature. Stirring is continued for a further 45 minutes and the excess nitrite then destroyed by addition of a small quantity of sulphamic acid. The orange suspension is then added to 23g of the solution of compound (100), obtained as described in Step 1 of Example 1, to which a further 120g of water and 2.5m1 of 2N aqueous sodium hydroxide solution had been added, the pH being maintained at 5.5 during the addition by simultaneous addition of a total of 8m1 of 2N aqueous sodium hydroxide solution.
After salting out, 3.6g of the compound of formula (102) are obtained which dyes paper with a high degree of exhaustion in brilliant scarlet shades with excellent water fastness.
If, in Step 1 of Example 1, after reaction of cyanuric chloride with N,N-diethylamino-propylamine, the 6-amino-1-naphthol-3-sulphonic acid is replaced by an equivalent quantity of 6-(4-aminobenzoyl)-amino-1-naphthol-3-sulphonic acid and proceeding in an analogous manner the intermediate of the formula O HN~~N~
N \ N- \ N ~ (100m) H H
~N N N N
H H
may be obtained.

By replacement of the 1-naphthylamine-6-sulphonic acid in Step 2 of Example 1 or of the 2-naphthylamine-7-sulphonic acid in Example 2, by an aromatic amine of the formula A'NH2, and proceeding in an analogous manner, either by reaction with the intermediate of formula (100) or (100m), the following dyes of the formula ~H
A~N~N \ \ HN~N~
/ /
H03S H N ~ i (12) N \N~N~~N~
H H
n may be obtained, as summarized in Table 2 below.

Table 2 . T- Exarnp . Nr. ' , . ' .. .~ ~.~_. ~ - : .. n.
_ _ . .. A °
~e _ .._.~

(103) ~ ~ ~ 0 (104) ~ ~ ~ 1 (105) ~ ~ ~ 0 (106) ~ ~ ~ 1 (107) ~ ~ ~ 0 / /

(108) ~ ~ ~ 1 (109) ~ ~ ~ 0 / /

(110) ~ ~ ~ 1 (111) ~ ~ ~ 0 / /

(112) ~ ~ ~ 1 / /

(113) I \ \ 0 i i (114) I \ \ 1 i i (115) ~ \ \ 0 i i (116) I \ \ 1 i i (117) I \ \ 0 i i (118) I \ \ 1 i i \ \ SOaH
(119) I ~ ~ 0 \ \ SOsH
(120) I ~ ~ 1 ( 121 ) ~ ~ so3H 0 (122) ~ ~ so,H 1 coZH
(123) I \ \ 0 i i OZH
(124) I \ \ 1 i i w w (125) I ~ ~ co2H 0 (126) I ~ ~ cozH

~ COZH
(127) I ~ ~ 0 ~ COZH
( 128) (129) 0 (130) 1 (131) 0 (132) (133) \ / 0 (134) \ / 1 ~ S03H
(135) 0 (136) 1 ( 137) 0 ci (138) 1 ci \ / S03H
(139) 0 OZN
\ / S03H
( 140) 1 (141) \ / 0 (142) \ / 1 OH
(143) \ / cH3 0 OH
(144) \ / cH3 1 (145) \ / °~ 0 (146) \ / °. 1 (147) \ / °" 0 (148) \ / off 1 OH
(149) \ / NHCOCH3 O

(150) \ / NHCOCH3 1 _ - H
(151) \ / NHZ 0 ° H
(152) \ / NH2 1 - ° H
(153) \ / N°Z 0 (154) \ / N°Z 1 H
(155) \ / ci 0 (156) \ / ci 1 ° H
(157) \ / 0 (158) \ / 1 (159) \ / 0 (160) \ / 1 (161) \ / 0 HO

(162) \ / 1 HO

(163) \ / 0 oz (164) \ / 1 OZN

(165) \ / 0 ci (166) \ / 1 ci (167) \ / c"3 0 (168) . \ / c"3 1 (169) \ / ~cH 0 (170) \ / NCH 1 (171 ) \ / NHCOCH3 0 (172) \ / NHCOCH3 1 (173) \ / N"~ 0 (174) / NHz 1 \

(175) / Nz 0 \

(176) Nz 1 \ /

\ / COZH

( 177) 0 \ / COzH

(178) 1 \ / COZH

( H3C
) \ / COzH

( H3C
) \ / CzH

( H3C-O
) \ / COZH

( HOC-O
) \ / COZH

( HO
) \ / CzH

(184) HO

\ / COZH

(185) 0 \ / C02H

(186) 1 \ / C02H

( ci ) \ / COzH

( ci ) COZH
1 \ / 0 ( O-CH3 ) COZH
\ / 1 (190) O-CH3 COZH
\ / 0 (191) OH

COzH
\ 1 /

(192) , OH

\ / COzH

(193) 0 NOZ

\ / COZH

( 194) 1 \ / 0 (195) NHZ

COzH
19 \ / 1 ( NHZ
6) co2H
(197) \ / 0 ci co2H
(198) \ / 1 ci OZH
(199) ~ ~ 0 OZH
(200) ~ ~ 1 (201 ) ~ ~ 0 (202) ~ ~ 1 (203) ~ ~ 0 OzH
(204) ~ ~ 1 (205) ~ ~ 0 HO

(206) ~ ~ 1 HO

OZH
(207) \ / 0 OZH
(208) \ / 1 OzH

(209) \ /
HZN
OzH
(210) \ / 1 HZN
OZH
(211 ) \ / 0 ci OZH
(212) \ / 1 ci OZH
(213) \ / off 0 OZH
(214) \ / off 1 02H ' (215) \ / NHz OZH
(216) \ / NHZ 1 OZH
(217) \ / No2 0 OH
(218) \ / N°2 1 OZH
(219) \ / c~ 0 OZH
(220) \ / ci 1 OzH
(221 ) \ / 0 (222) \ / 1 OZH
(223) \ / 0 NHZ

(224) NHz OZH
(225) \ / 0 NOZ

(226) ' \ /
NOZ

HO OzH
(227) \ / 0 HO OZH
(228) \ / 1 HaC OzH
(229) \ / 0 HaC OzH
(230) \ / 1 - off (231 ) \ / 0 ci °2H
(232) \ / 1 HoZc (233) \ / 0 HoZc (234) \ / 1 Ho2c (235) \ / CHa 0 Ho2c (236) \ / cHa 1 Ho2c (237) \ / ~cH 0 HOzC
(238) \ / ~cH 1 "oZc (239) \ / °" 0 "o2c (240) \ / °" 1 "oZc (241) \ / NHCOCH3 O
"o2c (242) \ / NHCOCH3 1 "02C
(243) \ / N"Z 0 "ozc (244) \ / N"2 1 "oZc (245) \ / NoZ 0 "oZc (246) \ / Noz 1 "o2c (247) \ / c~ 0 "o2c (248) \ / c~ 1 "oZc (249) \ / 0 HOZC
(250) \ / 1 Ho2c (251) \ /
H~c-o HoZc (252) \ / 1 HOZC
(253) \ / 0 HO
HOZC
(254) \ / 1 HO
HOZC
(255) \ / 0 HoZc (256) \ / 1 OZN

(257) \ / 0 ci Ho,c (258) \ / 1 ci (259) \ / 0 (260) \ / 1 (261 ) \ / 0 (262) \ / 1 Ho2c (263) \ / cH3 0 (264) \ / cH3 1 (265) \ / 0 HOzC CH3 (266) \ / 1 HOZC

(267) \ / ° 0 HOZC

(268) \ / ° 1 HOZC
(269) \ / 0 HOZC
(270) \ / 1 HOZC
(271 ) \ / c~ 0 ci Ho2c (272) \ / c~
ci HoZc ci (273) \ / 0 ci HoZc ci (274) \ / 1 ci If, in Step 1 of Example 1, after reaction of cyanuric chloride with N,N-diethylamino-propylamine, the 6-amino-1-naphthol-3-sulphonic acid is replaced by an equivalent quantity either of 7-amino-1-naphthol-3-sulphonic acid or of 7-(4-aminobenzoyl)-amino-1-naphthol-3-sulphonic acid and proceeding in an analogous manner, the corresponding intermediates of the formulae H03S ~ OH HN~~N~
N ~N
(100n) and N N N N
H H
OH
%' O HN N
N ~ N' \ N ~ (100p) N N N N
H H
may be obtained.

By replacement of the 1-naphthylamine-6-sulphonic acid in Step 2 of Example 1 or of the 2-naphthylamine-7-sulphonic acid in Example 2, by an aromatic amine of the formula A"NH2, and proceeding in an analogous manner, either by reaction with the intermediate of formula (100n) or (100p), the following dyes of the formula H H
N I N~N~N~
O \~H
H
A~~N%N \ \ N N N (13) HN~N~

may be obtained, as summarized in Table 3 below.

Table 3 Example Nr. 'A" _ n (275) ~ ~ ~ 0 (276) ~ ~ ~ 1 (277) ~ ~ ~ 0 so3H
(278) ~ ~ ~ 1 ~ S03H
(279) ~ ~ ~ 0 l l S03H .
(280) ~ ~ ~ 1 (281) ~ ~ ~ 0 l (282) ~ ~ ~ 1 (283) ( ~ ~ 0 (284) ~ ~ ~ 1 (285) I ~ ~ 0 / /

(286) I ~ ~ 1 / /

(287) I ~ ~ 0 / /

(288) I ~ ~ 1 / /

(289) I w w 0 / /

(290) I ~ ~ 1 / /
~ S03H
(291 ) I / ~ 0 ~ S03H
(292) I / / 1 (293) ~ / so3H 0 (294) / / so,H 1 (295) I ~ ~ 0 / /
OZH
(296) I ~ ~ 1 / /

(297) ~ ~ coZH 0 (298) I ~ ~ co2H 1 ~ C02H
(299) I ~ ~ 0 ~ COZH
(300) I i i 1 (301) 0 (302) 1 (303) 0 (304) 1 (305) \ ~ 0 (306) 1 (307) 0 (308) 1 (309) 0 O

(310) 1 ci \ / SOaH
(311 ) oZN 0 \ / SOaH
(312) 1 OZN

(313) \ / 0 (314) \ / 1 (315) \ / cH, 0 O H
(316) \ / cH3 1 OH
(317) \ / °. 0 (318) \ / °. 1 (319) \ / off 0 O H
(320) \ / off 1 OH
(321) \ / NHCOCH3 O

(322) \ / NHCOCH3 1 - OH
(323) \ / NHZ 0 OsH
(324) \ / NHZ 1 (325) \ / No2 0 O H
(326) \ / No2 1 (327) \ / c~ 0 OH
(328) \ / c~ 1 OH
(329) \ / 0 HOC

(330) \ / 1 (331) H,c-o (332) \ / 1 (333) \ / 0 HO

(334) \ / 1 HO

(335) \ / 0 OZN

(336) \ / 1 (337) \ / 0 ci (338) \ / 1 ci (339) \ / °"3 0 (340) \ / cH3 1 (341) \ / ~cH 0 (342) \ / ~cH

(343) \ / NHCOCH3 0 (344) \ / NHCOCH3 1 (345) \ / NHz 0 (346) NHz 1 \ /

(347) N2 0 \ /

(348) / N2 1 \

\ / COZH

(349) 0 \ / COxH

(350) 1 \ / COzH
351 ' 0 ) H3C
( \ / COzH

(352) H3C

\ / COzH

( H3C-O
) \ / COxH

) HOC-O
(35 \ / COZH

( HO
) \ / COzH

35g HO
( ) \ / COxH

(357) 0 oz \ / COxH

(358) 1 oz \ / COzH

( ci ) \ / COxH

( a ) COZH
361 \ / 0 ( O-CH3 ) COZH
\ / 1 (362) O-CH3 COZH
\ / 0 (363) OH

COZH
4 \ / 1 ) off (36 COZH
\ /

(365) 0 NOZ

\ / COxH

(366) 1 NOZ

\ / 0 (367) NH2 COZH
\ / 1 (368) NHz co,H
(369 \ / 0 ) ci cozH
(370) \ /
ci 1 OzH
(371 ) \ / 0 OzH
(372) \ / 1 OzH
(373) \ / 0 OZH
(374) \ / 1 OZH
(375) \ / 0 OZH
(376) \ / 1 OzH
(377) \ / 0 HO

(378) \ / 1 HO

(379) \ / 0 OZH
(380) \ / 1 O H
(381 ) \ / 0 O H
(382) \ / 1 HZN
OZH
(383) \ / 0 ci (384) \ / 1 ci OZH
(385) \ / off 0 (386) \ / off 1 OZH
(387) \ / NHZ 0 O H
(388) \ / NH2 1 OZH
(389) \ / No2 0 OZH
(390) \ / N°2 1 OH
(391 ) \ / o~ 0 O H
(392) \ / ci 1 OZH
(393) \ / 0 OZH
(394) \ /

OzH
(395) \ / 0 NHZ

(396) \ / 1 NHZ
OZH
(397) \ / 0 NOz OZH
(398) \ / 1 HO OzH
(399) \ / 0 HO OzH
(400) \ / 1 HsC OZH
(401) \ / 0 HsC OzH
(402) \ / 1 off (403) \ / 0 ci oZH
(404) \ / 1 HoZc (405) \ / 0 (406) \ / 1 Ho2c (407) \ / cH3 0 HoZc (408) \ / c"3 1 HOaC
(409) \ / ~cH 0 (410) \ / ~cH 1 HoZc (411 ) \ / °" 0 HOZC
(412) \ / °" 1 HoZc (413) \ / NHCOCH3 O
Ho2c (414) \ / NHCOCH3 1 HoZc (415) \ / NHZ 0 Ho2c (416) \ / NHZ 1 HoZc (417) \ / N°2 0 Ho2c (418) \ / N°2 1 Ho2c (419) \ / c~ 0 Ho2c (420) \ / c~ 1 Hozc (421) \ / 0 (422) \ / 1 HOZC
(423) ~ / 0 HOZC
(424) ~ / 1 (425) ~ / 0 HO

(426) ~ / 1 HO
HOZC
(427) ~ / 0 (428) ~ / 1 HOZC
(429) ~ / 0 ci Ho2c (430) ~ / 1 ci (431) ~ / 0 (432) ~ / 1 HOzC O-CH3 (433) ~ / 0 (434) \ / 1 Ho2c (435) \ / cH3 0 (436) \ / cH3 1 (437) \ / 0 (438) \ / 1 HOZC

(439) \ / ° 0 HOZC

(440) \ / 0 1 HOZC
(441) \ / 0 HOZC
(442) \ / 1 (443) \ / c~ 0 ci Ho2c (444) \ / c~ 1 ci Ho2c ci (445) \ / 0 ci Ho2c ci (446) \ / 1 ci

Claims

1. A compound of the formula in which A represents a benzene sulphonic acid residue which is unsubstituted or substituted by one single hydroxy, halogen, amino, nitro, C1-C4alkyl, C1-C4alkoxy, C2-C4hydroxyalkoxy, COOC1-C4alkyl or NHCOC1-C4alkyl group, a benzoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C1-C4alkyl, C1-C4alkoxy, C2-C4hydroxyalkoxy, COOC1-C4alkyl or NHCOC1-C4alkyl groups, a naphthalene sulphonic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C1-C4alkyl, C1-C4alkoxy, C2-C4hydroxyalkoxy, COOC1-C4alkyl or C4alkyl groups or a naphthoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C1-C4alkyl, C1-C4alkoxy, C2-C4hydroxyalkoxy, COOC1-C4alkyl or NHCOC1-C4alkyl groups;
D1 and D2, independently represent i) a residue of the formula -NR1BX (3), in which B represents a C2-C8alkylene bridge which may be interrupted by a heteroatom, whereby C3-C8alkylene is branched or unbranched, a C2-C8alkylene bridge which is substituted by one or more hydroxy groups, a C1-C6alkylene-1,3- or -1,4-phenylene bridge or a 1,3-or -1,4-phenylene bridge;
R1 represents hydrogen or C1-C4alkyl unsubstituted or mono-substituted by hydroxy, halogen, cyano or C1-C4alkoxy;
X is a group of the formula -NR2R3, wherein R2 and R3, independently, represent hydrogen, C1-C4alkyl, C2-C6alkyl which is mono-substituted by hydroxy or by cyano, phenyl or C1-C4alkylphenyl, whereby the phenyl ring of the latter two groups is unsubstituted or substituted by up to three groups selected from hydroxy, halogen, C1-C4alkyl and C1-C4alkoxy or, alternatively, R2 and R3, together with the nitrogen atom to which they are connected, complete a saturated, 5- or 6-membered ring which may contain, in addition to the nitrogen atom, one nitrogen or oxygen atom and which may be further substituted or, alternatively, X is a group of the formula -N+R4R5R6, wherein R4, R5 and R6 each, independently, represent C1-C4alkyl, C2-C6alkyl which is mono-substituted by hydroxy or by cyano, phenyl or C1-C4alkylphenyl, whereby the phenyl ring of the latter two groups is unsubstituted or substituted by up to three groups selected from hydroxy, halogen, C1-C4alkyl and C1-C4alkoxy or, ii) alternatively, D1 and D2, independently represent a 5- or 6-membered, saturated heterocyclic ring connected by way of a nitrogen atom to the triazine ring and which ring may contain, in addition to the nitrogen atom, one further nitrogen or oxygen atom and which may be further substituted, whereby the nitrogen atom may be quaternised with a residue R4 or be substituted with a C2-C6alkyltrialkylammonium residue, R4 being as previously defined, and n is 0 or 1, the compound being in an internal or external salt form, or mixtures of compound (1 ) and (2).

2. A compound according to claim 1 in which D1 and D2 are identical.

3. A compound according to claim 1 or claim 2 in which A represents a benzene sulphonic acid group which is unsubstituted or substituted by one single amino, nitro, halogen, hydroxy, C1-C4alkyl, C1-C4alkoxy or NHCOC1-C4alkyl group, a benzoic acid residue which is unsubstituted or substituted by one or more hydroxy, halogen, amino, nitro, C1-C4alkyl, C1-C4alkoxy or NHCOC1-C4alkyl groups, a naphthalene sulphonic acid residue or a naphthoic acid residue.

4. A compound according to claim 3 in which A represents a 1-naphthalene-2-, 3-, 4-, 6-, 7- or 8- or a 2-naphthalene-1-, 5-, 6- or 7-sulphonic acid residue.

5. A compound according to claim 3 in which A represents a benzene-2-, -3- or -4-sulphonic acid residue which is unsubstituted or substituted by one amino, acetylamino, chloro, hydroxy, nitro, methyl or methoxy group.

6. A compound according to claim 3 in which A represents a 2-, 3- or 4-benzoic acid residue which is unsubstituted or substituted by one or two acetylamino, hydroxy, chloro, amino, nitro, methyl or methoxy groups.

7. A compound according to claim 3 in which A represents a 2-substituted 1- or 3-naphthoic acid residue.

8. A compound according to any one of claims 1 to 7 in which B represents a C2-C6alkylene bridge which is unbranched or, in the case of C3-C6alkylene, branched, and which may be substituted by a hydroxy group, R1 represents hydrogen or C1-C4alkyl and X is a group of the formula NR2R3 or -N+R4R5R6, wherein R2 and R3, independently, represent hydrogen or C1-C4alkyl and R4, R5 and R6 each, independently, represent C1-C4alkyl.

9. A compound according to claim 8 in which B represents a C2-C4alkylene bridge which is unbranched or, in the case of C3-C4alkylene, branched, and may be substituted by a hydroxy group, R1 represents hydrogen or methyl and X is a group of the formula NR2R3 or -N+R4R5R6, wherein R2 and R3 both represent hydrogen, methyl or ethyl and R4, R5 and R6 each represent methyl or ethyl.

10. A compound according to any one of claims 1 to 7 in which D1 and D2 represent an -N-pyrrolidino, -N-morpholino, -N-piperidno or -N-piperazino residue, whereby the piperazino ring may be further substituted by C1-C4alkyl, C1-C4aminoalkyl or C1-C4hydroxyalkyl on the nitrogen atom in the 4-position.

11. A compound of formula (1), according to claim 1, in which A represents a 1-naphthalene-6-sulphonic acid, a 2-naphthalene-6-sulphonic acid or a 2-naphthalene-7-sulphonic acid residue, B represents an n-propylene or an isopropylene residue, R1 represents hydrogen, X is a diethylamino or an amino residue and n is 0, the compound being in an internal or external salt form.

12. A process for the preparation of the compound of formula (1) or of formula (2), according to claim 1, comprising reacting the diazonium salt of an amine of the formula A-NH2 (4) with a compound of the formula whereby A, R1, D1, D2 and n are as defined in claim 1.

13. A solid dye preparation for dyeing paper, comprising a compound of the formula (1) and/or (2), according to claim 1, and further auxiliaries.

14. Aqueous solutions for dyeing paper, comprising a compound of the formula (1) and/or (2), according to claim 1, and, optionally, further auxiliaries.

15. Aqueous solutions according to claim 14 containing, as further auxiliaries, solubilizers and/or organic solvents.

16. Paper which is dyed with a compound of the formula (1) and/or (2), according to claim 1, in the form of a solid dye preparation, according to claim 13, or an aqueous solution, according to claim 14.